Spectroscopic and theoretical considerations of cyclopropenone

Please consult the paper edition of this thesis to read. It is available on the 5th Floor of the Library at Call Number: Z 9999 P65 D53 2007The absorption spectrum of cyclopropenone has been photographically recorded under conditions of long pathlength (60 m), and moderate resolution (7.8 A/rom). The absorption was assigned to the electron promotion, n --> pi* (C=O) , and to the electronic transition B1As -- X1A1. The spectrum proved to be limited in band structure, which hindered the vibrational calculated for the X1A1, a3B1, and b3A2 states at the 6-31g* Hartree-Fock level. The calculations confirmed the assigned transition and predicted the position and structure of the second a3Bl1 system

Antioxidant enzymes in the developing lungs of egg-laying and metamorphosing vertebrates

© The Company of BiologistsThe activities of the pulmonary antioxidant enzymes (AOE), superoxide dismutase (SOD), glutathione peroxidase (GPx) and catalase, increase in the final 10–20 % of gestation in the mammalian lung, to protect the lung from attack by increasing levels of reactive oxygen species at birth. Whether the increase occurs as a normal ‘preparation for birth’, i.e. by a genetically determined mechanism, or in response to increased levels of oxygen, i.e. in response to the environment, is not completely understood. We examined the activities of catalase, SOD and GPx in the developing lungs of two oviparous vertebrate species, the chicken (Gallus gallus) and an agamid lizard (Pogona vitticeps), and in a metamorphosing vertebrate, the anuran Limnodynastes terraereginae. During in ovo development embryos come into contact with higher levels of environmental oxygen, and at a much earlier stage of development, compared with the intrauterine development of mammals. Furthermore, in metamorphosing frogs, the lungs are inflated at an early stage to aid in buoyancy, although the gas-exchange function only develops much later upon final metamorphosis. Here, we hypothesise that the activity of the AOE will be elevated relatively much earlier during development in both oviparous and metamorphosing vertebrates. We also examined the effect of mild hypoxia (17 % oxygen) on the development of the pulmonary AOE in the chicken, to test the hypothesis that these enzymes are responsive to environmental oxygen. In the normoxic lung of both Gallus gallus and Pogona vitticeps, catalase and GPx activities were significantly increased in late incubation, whereas SOD activity decreased in late incubation. Catalase and SOD activities were virtually identical in hypoxic and normoxic embryos of the chicken, but GPx activity was significantly affected by hypoxia. In the developing frog, the activities of all enzymes were high at stage 30, demonstrating that the system is active before the lung displays any significant gas-exchange function. SOD and GPx activity did not increase further with development. Catalase activity increased after stage 40, presumably correlating with an increase in air-breathing. In summary, catalase expression in the two oviparous vertebrates appears to be completely under genetic control as the activity of this enzyme does not change in response to changes in oxygen tension. However, in tadpoles, catalase may be responsive to environmental oxygen. SOD also appears to follow a largely genetically determined program in all species. Under normoxic conditions, GPx appears to follow a genetically determined developmental pattern, but this enzyme demonstrated the largest capacity to respond to environmental oxygen fluctuations. In conclusion, it appears that the AOE are differentially regulated. Furthermore, the AOE in the different species appear to have evolved different levels of dependency on environmental variables. Finally, the late developmental increase in AOE activity seen in mammals is not as pronounced in oviparous and metamorphosing vertebrates.Adam P. Starrs, Sandra Orgeig, Christopher B. Daniels, Margaret Davies and Olga V. Lopatk

Microrheology, stress fluctuations and active behavior of living cells

We report the first measurements of the intrinsic strain fluctuations of living cells using a recently-developed tracer correlation technique along with a theoretical framework for interpreting such data in heterogeneous media with non-thermal driving. The fluctuations' spatial and temporal correlations indicate that the cytoskeleton can be treated as a course-grained continuum with power-law rheology, driven by a spatially random stress tensor field. Combined with recent cell rheology results, our data imply that intracellular stress fluctuations have a nearly $1/\omega^2$ power spectrum, as expected for a continuum with a slowly evolving internal prestress.Comment: 4 pages, 2 figures, to appear in Phys. Rev. Let

Donor–acceptor co-adsorption ratio controls the structure and electronic properties of two-dimensional alkali–organic networks on Ag(100)

P.T.P.R. and P.J.B. acknowledge financial support from Diamond Light Source and EPSRC. G.C. acknowledges financial support from the EU through the ERC Grant “VISUAL-MS” (Project ID: 308115). B.S. and R.J.M. acknowledge doctoral studentship funding from the EPSRC and the National Productivity Investment Fund (NPIF). R.J.M. acknowledges financial support via a UKRI Future Leaders Fellowship (MR/S016023/1).The results are presented of a detailed combined experimental and theoretical investigation of the influence of coadsorbed electron-donating alkali atoms and the prototypical electron acceptor molecule 7,7,8,8-tetracyanoquinodimethane (TCNQ) on the Ag(100) surface. Several coadsorption phases were characterized by scanning tunneling microscopy, low-energy electron diffraction, and soft X-ray photoelectron spectroscopy. Quantitative structural data were obtained using normal-incidence X-ray standing wave (NIXSW) measurements and compared with the results of density functional theory (DFT) calculations using several different methods of dispersion correction. Generally, good agreement between theory and experiment was achieved for the quantitative structures, albeit with the prediction of the alkali atom heights being challenging for some methods. The adsorption structures depend sensitively on the interplay of molecule–metal charge transfer and long-range dispersion forces, which are controlled by the composition ratio between alkali atoms and TCNQ. The large difference in atomic size between K and Cs has negligible effects on stability, whereas increasing the ratio of K/TCNQ from 1:4 to 1:1 leads to a weakening of molecule–metal interaction strength in favor of stronger ionic bonds within the two-dimensional alkali–organic network. A strong dependence of the work function on the alkali donor–TCNQ acceptor coadsorption ratio is predicted.Publisher PDFPeer reviewe

Optical microrheology using rotating laser-trapped particles

We demonstrate an optical system that can apply and accurately measure the torque exerted by the trapping beam on a rotating birefringent probe particle. This allows the viscosity and surface effects within liquid media to be measured quantitatively on a micron-size scale using a trapped rotating spherical probe particle. We use the system to measure the viscosity inside a prototype cellular structure.Comment: 5 pages, 4 figures. v2: bibliographic details, minor text correction

Predicting suicides after outpatient mental health visits in the Army Study to Assess Risk and Resilience in Servicemembers (Army STARRS).

The 2013 US Veterans Administration/Department of Defense Clinical Practice Guidelines (VA/DoD CPG) require comprehensive suicide risk assessments for VA/DoD patients with mental disorders but provide minimal guidance on how to carry out these assessments. Given that clinician-based assessments are not known to be strong predictors of suicide, we investigated whether a precision medicine model using administrative data after outpatient mental health specialty visits could be developed to predict suicides among outpatients. We focused on male nondeployed Regular US Army soldiers because they account for the vast majority of such suicides. Four machine learning classifiers (naive Bayes, random forests, support vector regression and elastic net penalized regression) were explored. Of the Army suicides in 2004-2009, 41.5% occurred among 12.0% of soldiers seen as outpatient by mental health specialists, with risk especially high within 26 weeks of visits. An elastic net classifier with 10-14 predictors optimized sensitivity (45.6% of suicide deaths occurring after the 15% of visits with highest predicted risk). Good model stability was found for a model using 2004-2007 data to predict 2008-2009 suicides, although stability decreased in a model using 2008-2009 data to predict 2010-2012 suicides. The 5% of visits with highest risk included only 0.1% of soldiers (1047.1 suicides/100 000 person-years in the 5 weeks after the visit). This is a high enough concentration of risk to have implications for targeting preventive interventions. An even better model might be developed in the future by including the enriched information on clinician-evaluated suicide risk mandated by the VA/DoD CPG to be recorded

Developments in Performance Monitoring of Concrete Exposed to Extreme Environments.

The performance of the surface zone of concrete is acknowledged as a major factor governing the rate of deterioration of reinforced concrete structures because it provides the only barrier to the ingress of water containing dissolved ionic species such as chlorides, which ultimately initiate corrosion of the reinforcement. In situ monitoring of cover-zone concrete is therefore critical in attempting to make realistic predictions as to the in-service performance of the structure. To this end, this paper presents developments in a remote interrogation system to allow for continuous, real-time monitoring of the cover-zone concrete from an office setting. Use is made of a multi electrode array embedded within cover-zone concrete to acquire discretized electrical resistivity and temperature measurements, with both parameters monitored spatially and temporally. On-site instrumentation, which allows for the remote interrogation of concrete samples placed at a marine exposure site, is detailed together with data handling and processing procedures. Site measurements highlight the influence of temperature on electrical resistivity and an Arrhenius-based temperature correction protocol is developed using on-site measurements to standardize resistivity data to a reference temperature; this is an advancement over the use of laboratory-based procedures. The testing methodology and interrogation system represent a robust, low-cost, and high-value technique that could be deployed for intelligent monitoring of reinforced concrete structures

Microrheology with optical tweezers: data analysis

We present a data analysis procedure that provides the solution to a long-standing issue in microrheology studies, i.e. the evaluation of the fluids' linear viscoelastic properties from the analysis of a finite set of experimental data, describing (for instance) the time-dependent mean-square displacement of suspended probe particles experiencing Brownian fluctuations. We report, for the first time in the literature, the linear viscoelastic response of an optically trapped bead suspended in a Newtonian fluid, over the entire range of experimentally accessible frequencies. The general validity of the proposed method makes it transferable to the majority of microrheology and rheology techniques

Thermodynamic Driving Forces for Substrate Atom Extraction by Adsorption of Strong Electron Acceptor Molecules

A quantitative structural investigation is reported, aimed at resolving the issue of whether substrate adatoms are incorporated into the monolayers formed by strong molecular electron acceptors deposited onto metallic electrodes. A combination of normal-incidence X-ray standing waves, low-energy electron diffraction, scanning tunnelling microscopy, and X-ray photoelectron spectroscopy measurements demonstrate that the systems TCNQ and F4TCNQ on Ag(100) lie at the boundary between these two possibilities and thus represent ideal model systems with which to study this effect. A room-temperature commensurate phase of adsorbed TCNQ is found not to involve Ag adatoms, but to adopt an inverted bowl configuration, long predicted but not previously identified experimentally. By contrast, a similar phase of adsorbed F4TCNQ does lead to Ag adatom incorporation in the overlayer, the cyano end groups of the molecule being twisted relative to the planar quinoid ring. Density functional theory (DFT) calculations show that this behavior is consistent with the adsorption energetics. Annealing of the commensurate TCNQ overlayer phase leads to an incommensurate phase that does appear to incorporate Ag adatoms. Our results indicate that the inclusion (or exclusion) of metal atoms into the organic monolayers is the result of both thermodynamic and kinetic factors